Assessment of selenium and zinc enriched sludge and duckweed as slow-release micronutrient biofertilizers for Phaseolus vulgaris growth.

Selenium (Se) and zinc (Zn) are essential micronutrients that are often lacking in the diet of humans and animals. Application of mineral Se and Zn fertilizers into soils may lead to a waste of Se and Zn due to the fast leaching and low utilization by plants. Slow-release Se and Zn biofertilizer may therefore be beneficial. This study aims to assess the potential of SeZn-enriched duckweed and sludge produced from wastewater as slow-release Se and Zn biofertilizers. Pot experiments with green beans (Phaseolus vulgaris) and sampling of Rhizon soil pore water were conducted to evaluate the bioavailability of Se and Zn in sandy and loamy soils mixed with SeZn-enriched duckweed and sludge. Both the Se and Zn concentrations in the soil pore water increased upon amending the two biomaterials. The concentration of Se released from SeZn-enriched duckweed rapidly decreased in the first 21 days and slowly declined afterwards, while it remained stable during the entire experiment upon application of SeZn-enriched sludge. The Zn content in the soil pore water gradually increased over time. The application of SeZn-enriched duckweed and sludge significantly increased the Se concentrations in plant tissues, in particular in the form of organic Se-methionine in seeds, without a negative impact on plant growth when an appropriate dose was applied (1 mg Se/kg soil). While, it did not increase Zn concentrations in plant seeds. The results indicate that the SeZn-enriched duckweed and sludge could be only used as organic Se biofertilizers for Se-deficient soils. Particularly, the SeZn-enriched sludge dominated with elemental nano-Se was an effective Se source and slow-release Se biofertilizer. These results could offer a theoretical reference to choose an alternative to chemical Se fertilizers for biofortification, avoiding the problem of Se losses by leaching from mineral Se fertilizers while recovering resources from wastewater. This could contribute to the driver for a future circular economy.

Selective copper recovery from ammoniacal waste streams using a systematic biosorption process.

Cu-NH3 bearing effluents arise from electroplating and metal extraction industries, requiring innovative and sustainable Cu recovery technologies to reduce their adverse environmental impact. CO32- and Zn are often co-occurring, and thus, selective Cu recovery from these complex liquid streams is required for economic viability. This study assessed 23 sustainable biosorbents classified as tannin-rich, lignin-rich, chitosan/chitin, dead biomass, macroalgae or biochar for their Cu adsorption capacity and selectivity in a complex NH3-bearing bioleachate. Under a preliminary screen with 12 mM Cu in 1 M ammoniacal solution, most biosorbents showed optimal Cu adsorption at pH 11, with pinecone remarkably showing high removal efficiencies (up to 68%) at all tested pH values. Further refinements on select biosorbents with pH, contact time, and presence of NH3, Zn and CO32- showed again that pinecone has a high maximum adsorption capacity (1.07 mmol g-1), worked over pH 5-12 and was Cu-selective with 3.97 selectivity quotient (KCu/Zn). Importantly, pinecone performance was maintained in a real Cu/NH3/Zn/CO32- bioleachate, with 69.4% Cu removal efficiency. Unlike synthetic adsorbents, pinecones require no pre-treatment, which together with its abundance, selectivity, and efficiency without the need for prior NH3 removal, makes it a competitive and sustainable Cu biosorbent for complex Cu-NH3 bearing streams. Overall, this study demonstrated the potential of integrating bioleaching and biosorption as a clean Cu recovery technology utilizing only sustainable resources (i.e., bio-lixiviant and biosorbents). This presents a closed-loop approach to Cu extraction and recovery from wastes, thus effectively addressing elemental sustainability.

Valorization of selenium-enriched sludge and duckweed generated from wastewater as micronutrient biofertilizer.

Selenium (Se) is an essential trace element for humans and animals with a narrow window between deficiency and toxicity levels. Application of conventional chemical Se fertilizers to increase the Se content of crops in Se deficient areas could result in environmental contamination due to the fast leaching of inorganic Se. Slow-release Se-enriched biofertilizers produced from wastewater treatment may therefore be beneficial. In this study, the potential of Se-enriched biomaterials (sludge and duckweed) as slow-release Se biofertilizers was evaluated through pot experiments with and without planted green beans (Phaseolus vulgaris). The Se concentration in the bean tissues was 1.1-3.1 times higher when soils were amended with Se-enriched sludge as compared to Se-enriched duckweed. The results proved that the Se released from Se-enriched biomaterials was efficiently transformed to health-beneficial selenoamino acids (e.g., Se-methionine, 76-89%) after being taken up by beans. The Se-enriched sludge, containing mainly elemental Se, is considered as the preferred slow-release Se biofertilizer and an effective Se source to produce Se-enriched crops for Se-deficient populations, as shown by the higher Se bioavailability and lower organic carbon content. This study could offer a theoretical reference to choose an environmental-friendly and sustainable alternative to conventional mineral Se fertilizers for biofortification, avoiding the problem of Se losses by leaching from chemical Se fertilizers while recovering resources from wastewater. This could contribute to the driver for a future circular economy.

Production of selenium-enriched microalgae as potential feed supplement in high-rate algae ponds treating domestic wastewater.

This study assessed the selenium (Se) removal efficiency of two pilot-scale high-rate algae ponds (HRAPs) treating domestic wastewater and investigated the production of Se-enriched microalgae as potential feed supplement. The HRAP-Se had an average Se, NH4+-N, total phosphorus and COD removal efficiency of, respectively, 43%, 93%, 77%, and 70%. Inorganic Se taken up by the microalgae was mainly (91%) transformed to selenoamino acids, and 49-63% of Se in the Se-enriched microalgae was bioaccessible for animals. The crude protein content (48%) of the microalgae was higher than that of soybeans, whereas the essential amino acid content was comparable. Selenium may induce the production of the polyunsaturated fatty acids omega-3 and omega-6 in microalgae. Overall, the production of Se-enriched microalgae in HRAPs may offer a promising alternative for upgrading low-value resources into high-value feed supplements, supporting the drive to a circular economy.

Selenate and selenite uptake, accumulation and toxicity in Lemna minuta.

The kinetics of Se uptake and toxicity to Lemna were studied over a period of 14 days of exposure to Se(IV) or Se(VI). The growth of Lemna stopped immediately after exposure to 5.0 mg/L of Se(IV) or Se(VI). The content of chlorophyll and phaeopigments of Lemna exposed to 5.0 mg/L of Se(IV) was two to three times less than in the control after 3 d exposure. Lemna took up Se rapidly within the first 3 d. The Se content in Lemna along with the exposure time fitted well the two-compartment and the hyperbolic model, which demonstrates that the mechanism of Se(IV) and Se(VI) uptake in Lemna is not only through passive diffusion, but also through other processes such as ion channel proteins or transporters. The kinetic bioconcentration factors (BCFs) were 231 and 42 for 0.5 mg/L Se(IV) and Se(VI) exposure, respectively. The uptake rate of Lemna reached 263 mg/kg/d and 28 mg/kg/d in the Se(IV) and Se(VI) treatments, respectively. This study showed that Se(IV) has a faster accumulation rate than Se(VI), but a higher toxicity, indicating Lemna could be a good candidate to remove Se(IV) from water, producing Se-enriched biomass which may eventually also be considered for use as Se-enriched feed supplement or fertilizer.

Production of selenium- and zinc-enriched Lemna and Azolla as potential micronutrient-enriched bioproducts.

Selenium (Se) and zinc (Zn) are essential micronutrients that are often lacking in the diet of humans and animals, leading to deficiency diseases. Lemna and Azolla are two aquatic plants with a substantial protein content, which offer the possibility of utilizing them to remove Se and Zn from (waste)water while producing micronutrient-enriched dietary proteins and fertilizers. In this study, we explored interaction effects occurring between Se and Zn when these micronutrients are taken up by Azolla and Lemna. The two aquatic plants were grown on hydroponic cultures containing 0-5.0 mg/L of Se (Se(IV) or Se(VI)) and Zn. The Se and Zn content of the plants, growth indicators, bioconcentration factor (BCF) and Se/Zn removal efficiency from the water phase were evaluated. The results demonstrated that Se(IV) is more toxic than Se(VI) for both plant species, as evidenced by the remarkable decrease of biomass content and root length when exposed to Se(IV). Both aquatic plants took up around 10 times more Se(IV) than Se(VI) from the medium. Moreover, the Se accumulation and removal efficiency increased by 66-99% for Se(IV) and by 34-59% for Se(VI) in Lemna when increasing Zn dosage from 0 to 5.0 mg/L in the medium, whereas it declined by 13-26% for Se(IV) and 21-35% for Se(VI) in Azolla, suggesting a synergetic effect in Lemna, but an antagonistic effect in Azolla. The maximum BCF of Se in Lemna and Azolla were 507 and 667, respectively. The protein content in freeze-dried Lemna and Azolla was approximately 17%. The high tolerance and accumulation of Se and Zn in Lemna and Azolla, combined with their rapid growth, high protein content and transformation of inorganic to organic Se species upon Se(IV) exposure make Lemna and Azolla potential candidates for the production of Se(IV)- and Zn-enriched biomass that can be used as crop fertilizers or protein-rich food/feed supplements or ingredients. Accordingly, by growing the Azolla and Lemna on wastewater, a high-value product can be produced from wastewater while recovering resources.

Novel nanostructured iron oxide cryogels for arsenic (As(III)) removal.

Novel macroporous iron oxide nanocomposite cryogels were synthesized and assessed as arsenite (As(III)) adsorbents. The two-step synthesis method, by which a porous nanonetwork of iron oxide is firstly formed, allowed a homogeneous dispersion of the iron oxide in the cryogel reaction mixture, regardless of the nature of the co-polymer forming the cryogel structure. The cryogels showed excellent mechanical properties, especially the acrylamide-based cryogel. This gel showed the highest As(III) adsorption capacity, with the maximum value estimated at 118 mg/g using the Langmuir model. The immobilization of the nanostructured iron oxide gel into the cryogel matrix resulted in slower adsorption kinetics, however the cryogels offer the advantage of a stable three-dimensional structure that impedes the release of the iron oxide nanoparticles into the treated effluent. A preliminary toxicity evaluation of the cryogels did not indicate any apparent inhibition of human hepatic cells activity, which together with their mechanical stability and high adsorption capacity for As(III) make them excellent materials for the development of nanoparticle based adsorption devices for drinking water treatment.

Recovery of palladium(II) by methanogenic granular sludge.

This is the first report that demonstrates the ability of anaerobic methanogenic granular sludge to reduce Pd(II) to Pd(0). Different electron donors were evaluated for their effectiveness in promoting Pd reduction. Formate and H2 fostered both chemically and biologically mediated Pd reduction. Ethanol only promoted the reduction of Pd(II) under biotic conditions and the reduction was likely mediated by H2 released from ethanol fermentation. No reduction was observed in biotic or abiotic assays with all other substrates tested (acetate, lactate and pyruvate) although a large fraction of the total Pd was removed from the liquid medium likely due to biosorption. Pd(II) displayed severe inhibition towards acetoclastic and hydrogenotrophic methanogens, as indicated by 50% inhibiting concentrations as low as 0.96 and 2.7 mg/L, respectively. The results obtained indicate the potential of utilizing anaerobic granular sludge bioreactor technology as a practical and promising option for Pd(II) reduction and recovery offering advantages over pure cultures.

Fate of fluorescent core-shell silica nanoparticles during simulated secondary wastewater treatment.

Increasing use of silica nanoparticles (SiO2 NPs) in consumer products and industrial processes leads to SiO2 NP discharge into wastewater. Thus, there is a need to understand the fate of SiO2 NPs during wastewater treatment. However, the detection of SiO2 NPs in environmental systems is hindered by the elevated background levels of natural silicon. In this work, laboratory-synthesized fluorescent core-shell SiO2 NPs were used to study the fate of these NPs during secondary wastewater treatment. Fluorescent measurements provided an easy and fast method for SiO2 NP tracking. A laboratory-scale activated sludge system consisting of an aeration tank and a settler was fed with synthetic wastewater containing ca. 7.5 mg L(-1) of fluorescent SiO2 NPs for 30 days. SiO2 NPs were effectively removed from the wastewater (>96%) during the first 6 days, however the concentration of SiO2 NPs in the effluent gradually increased afterwards and the NP discharge was as high as 65% of the input after 30 days of NP dosing. The poor removal of the SiO2 NPs was related to the high colloidal stability of the NPs in the wastewater and their limited propensity to biosorption. Although some degree of NP adsorption on the biomass was observed using fluorescence microscopy, the affinity of SiO2 NPs for the activated sludge was not enough for a sustained and effective removal of the SiO2 NPs from the wastewater.

Stability of alumina, ceria, and silica nanoparticles in municipal wastewater.

Inorganic oxide nanoparticles (NPs) are used in semiconductor manufacturing operations such as wafer chemical-mechanical planarization (CMP). Understanding the stability of NPs in municipal wastewater is essential for the evaluation of the fate of NPs released to municipal wastewater treatment plants (WWTPs). This study aimed to evaluate the stability of Al(2)O(3), CeO(2), and SiO(2) NPs and CMP waste effluents containing these NPs in municipal wastewater. Al(2)O(3) and CeO(2) NPs were destabilized by wastewater constituents, as indicated by the formation of large agglomerates. However, the same NPs in the CMP waste slurries showed high stability in wastewater, probably due to additives present in the slurry that modify the surface chemistry of the particles. Likewise, both the commercial SiO(2) NPs and the CMP waste slurry containing SiO(2) NPs showed substantial stability in wastewater since this NP has a very low point of zero charge, which suggests that this NP could be the hardest one to remove in conventional WWTPs by aggregation-sedimentation. In summary, the results indicate that wastewater may destabilize NPs suspensions, which would facilitate NP removal in WWTPs. However, some chemicals present in real CMP slurries may counterbalance this effect. More research is needed to completely understand the surface chemistry involved.

Inhibition of anaerobic wastewater treatment after long-term exposure to low levels of CuO nanoparticles.

CuO nanoparticles (NPs) are released into wastewater due to the widespread use and generation as by-product in various applications (e.g. semiconductor manufacturing). However, information on the behavior and impact of CuO NPs on wastewater treatment processes is very limited. The objective of this study was to evaluate the fate and long-term effect of CuO NPs (average size = 37 nm) on high-rate anaerobic bioreactors. A laboratory-scale upflow anaerobic sludge blanket reactor was operated with a synthetic wastewater containing low concentrations of CuO NPs (1.4 mg Cu L(-1)) and a mixture of volatile fatty acids for 107 days. CuO NPs were largely removed during anaerobic treatment and on the average only 20-32% of the NPs fed to the reactor escaped with the effluent. Scanning electron microscopy and chemical analysis confirmed that CuO NPs were partitioned into the anaerobic sludge. While short-term exposure to CuO NPs (1.4 mg Cu L(-1)) only caused minor inhibition to methanogenesis, extended exposure caused severe toxicity and reduced the acetoclastic methanogenic activity by more than 85%. Moreover, the reactor performance was completely disrupted and the methane production decreased by more than 50%. The study is the first to demonstrate a significant long-term effect of low levels of CuO NPs on methanogenesis.

Fate and long-term inhibitory impact of ZnO nanoparticles during high-rate anaerobic wastewater treatment.

The aim of this study was to evaluate the long-term effect of ZnO nanoparticles (NPs) on the performance of high-rate anaerobic bioreactors. Laboratory-scale upflow anaerobic sludge blanket (UASB) reactors were fed with a mixture of volatile fatty acids and exposed to either low (0.32 mg Zn L(-1)) or high (34.5 mg Zn L(-1)) concentrations of ZnO NPs. Exposure to high NP concentrations caused a rapid and permanent decline in the methane production and the removal of acetate and propionate. In contrast, a gradual and partial inhibitory response was observed in the reactor exposed to low NP concentrations. The long-term effect of the NP exposure was also evident from a decline in the specific methanogenic activity, which was more severe for the acetoclastic compared to the hydrogenotrophic methanogens. ZnO NPs were removed by 62-82% during passage through the UASB reactors. The results taken as a whole indicate that ZnO NPs cause severe inhibition of acetoclastic methanogens. Even sub-ppm levels of the nano-ZnO in the influent had a negative impact on the performance of the UASB reactor due to long-term exposure of methanogens to NPs that accumulated in the sludge bed.

Toxicity of TiO2, ZrO2, Fe°, Fe2O3, and Mn2O3 nanoparticles to the yeast, Saccharomyces cerevisiae.

The growing application of engineered nanomaterials is leading to an increased occurrence of nanoparticles (NPs) in the environment. Thus, there is a need to better understand their potential impact on the environment. This study evaluated the toxicity of nanosized TiO2, ZrO2, Fe(0), Fe2O3, and Mn2O3 towards the yeast Saccharomyces cerevisiae based on O2 consumption and cell membrane integrity. In addition, the state of dispersion of the nanoparticles in the bioassay medium was characterized. All the nanomaterials showed high tendency to aggregate in the bioassay medium. A non-toxic polyacrylate dispersant was used to improve the NP dispersion stability and test the influence of the aggregation state in their toxicity. Mn2O3 NPs showed the highest inhibition of O2 consumption (50% at 170 mg L(-1)) and cell membrane damage (approximately 30% of cells with compromised membrane at 1000 mg L(-1)), while the other NPs caused low (Fe(0)) or no toxicity (TiO2, ZrO2, and Fe2O3) to the yeast. Dispersant supplementation decreased the inhibition caused by Mn2O3 NPs at low concentrations, which could indicate that dispersant association with the particles may have an impact on the interaction between the NPs and the cells.

Biodegradability, cytotoxicity, and physicochemical treatability of two novel perfluorooctane sulfonate-free photoacid generators.

There is a need for effective, environmentally compatible photoacid generators (PAGs) for application in photolithography for microelectronic device fabrication. Perfluoroalkyl sulfonates (PFAS) used in conventional PAG formulations, such as perfluorooctane sulfonate (PFOS), are under increasing scrutiny due to their widespread environmental distribution and toxicity. Recently, two new PFAS-free, PAG anions with semifluorinated sulfonate anions containing biomolecules (γ-butyrolactone or D-glucose groups) were successfully applied as PAGs. In this study, the biodegradation potential, cytotoxicity, and physicochemical treatability of the new PAG anions was evaluated. PFOS and perfluorobutane sulfonate (PFBS) were used as reference materials in all of the assays. The new PAGs were susceptible to partial degradation by microorganisms in aerobic activated sludge, and these were also readily removed by chemical oxidative treatment with Fenton's reagent [H(2)O(2)/Fe(II)]. In contrast, the compounds were resistant to microbial and chemical attack under reductive conditions as indicated by the low removal efficiencies observed with anaerobic biodegradation assays and chemical assays with zero-valent iron, respectively. The enhanced biodegradation potential and treatability make of the new PAGs attractive materials to resolve current issues related to the lithographic performance and environmental concerns.

Application and validation of an impedance-based real time cell analyzer to measure the toxicity of nanoparticles impacting human bronchial epithelial cells.

Nanomaterials are increasingly used in a variety of industrial processes and consumer products. There are growing concerns about the potential impacts for public health and environment of engineered nanoparticles. The aim of this work was to evaluate a novel impedance-based real time cell analyzer (RTCA) as a high-throughput method for screening the cytotoxicity of nanoparticles and to validate the RTCA results using a conventional cytotoxicity test (MTT). A collection of 11 inorganic nanomaterials (Ag(0), Al(2)O(3), CeO(2), Fe(0), Fe(2)O(3), HfO(2), Mn(2)O(3), SiO(2), TiO(2), ZnO, and ZrO(2)) were tested for potential cytotoxicity to a human bronchial epithelial cell, 16HBE14o-. The data collected by the RTCA system was compared to results obtained using a more traditional methyl tetrazolium (MTT) cytotoxicity assay at selected time points following application of nanomaterials. The most toxic nanoparticles were ZnO, Mn(2)O(3) and Ag(0), with 50% response at concentrations lower than 75 mg/L. There was a good correlation in cytotoxicity measurements between the two methods; however, the RTCA method maintained a distinct advantage in continually following cytotoxicity over time. The results demonstrate the potential and validity of the impedance-based RTCA technique to rapidly screen for nanoparticle toxicity.

Low toxicity of HfO2, SiO2, Al2O3 and CeO2 nanoparticles to the yeast, Saccharomyces cerevisiae.

Increasing use of nanomaterials necessitates an improved understanding of their potential impact on environment health. This study evaluated the cytotoxicity of nanosized HfO(2), SiO(2), Al(2)O(3) and CeO(2) towards the eukaryotic model organism Saccharomyces cerevisiae, and characterized their state of dispersion in bioassay medium. Nanotoxicity was assessed by monitoring oxygen consumption in batch cultures and by analysis of cell membrane integrity. CeO(2), Al(2)O(3), and HfO(2) nanoparticles were highly unstable in yeast medium and formed micron-sized, settleable agglomerates. A non-toxic polyacrylate dispersant (Dispex A40) was used to improve nanoparticle stability and determine the impact of enhanced dispersion on toxicity. None of the NPs tested without dispersant inhibited O(2) uptake by yeast at concentrations as high as 1000 mg/L. Dispersant supplementation only enhanced the toxicity of CeO(2) (47% at 1000 mg/L). Dispersed SiO(2) and Al(2)O(3) (1000 mg/L) caused cell membrane damage, whereas dispersed HfO(2) and CeO(2) did not cause significant disruption of membrane integrity at the same concentration. These results suggest that the O(2) uptake inhibition observed with dispersed CeO(2) NPs was not due to reduced cell viability. This is the first study evaluating toxicity of nanoscale HfO(2), SiO(2), Al(2)O(3) and CeO(2) to S. cerevisiae. Overall the results obtained demonstrate that these nanomaterials display low or no toxicity to yeast.